TW200947492A - Electron discharge element, electron discharge device, self-luminous device, image display device, blower device, cooling device, charging device, image forming apparatus, electron beam curing device, and method for manufacturing electron discharge eleme - Google Patents

Abstract

An electron emitting element (1) comprises a substrate (2), an upper electrode (3) and a particle layer (4) formed between the substrate (2) and the upper electrode (3). The particle layer (4) contains metal particles (6) having a high oxidation resistance and insulating particles (5) having sizes larger than those of the metal particles (6). The electron emitting element (1) emits electrons stably in vacuum and even in the atmosphere, hardly produces harmful substances such as ozone and NOx because the electron emitting element (1) involves no electric discharge, and is not oxidized and deteriorated. Hence, the electron emitting element (1) can continuously operate stably for a long period of time even in the atmosphere and has a long service life.

Description

200947492 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to an electron emission element that can emit electrons by applying a voltage. [Prior Art] As a conventional electron emission element, a Spindt type electrode, a carbon nanotube (CNT) type electrode or the like is known. Such electronic emission components are applied, for example, in the field of FED (Field Emission Display). Such an electron emission element applies a voltage to a sharp-shaped portion to form a strong electric field of about 1 GV/m, and emits electrons by a tunneling effect. Further, there has been a demand for the above-described electron emission element to operate in the atmosphere, for example, there is a case where it is intended to be applied to a charging device or an electrostatic latent image forming device. In the example of the electron emission element of the Spindt type electrode, an example is proposed in which it is operated in the atmosphere, and electrons are emitted in the atmosphere, and the gas molecules are ionized to generate ions as charged particles, thereby forming an electrostatic latent image. (For example, refer to Patent Document 1), or a report on the research results of the operation of the electron emission element of the carbon nanotube type electrode in the atmosphere (for example, refer to Non-Patent Document 1). However, in the two types of electron emission elements, as described above, a strong electric field is formed in the vicinity of the surface of the electron emission portion, so that the emitted electrons obtain a large energy under the action of the electric field, and the gas molecules are easily ionized. The cations produced by the ionization of gas molecules accelerate the collision in the direction of the surface of the element under the action of a strong electric field, and there is a problem of component damage due to demining. 136193.doc 200947492. Moreover, the dissociation energy of oxygen in the atmosphere is lower than that of ionization energy, so ozone is generated before ions are generated. Ozone is harmful to the human body, and its strong oxidizing power causes oxidation of various substances, so there is a problem of damage to components around the component. In order to avoid the above problems, the following restrictions are imposed, that is, the peripheral member must use a material having high ozone resistance. .

On the other hand, as another electron emission element different from the above type, an MIM (Metal Insulator Metal) i or MlS (Metal Insulator Semiconductor's metal insulator semiconductor) type electron emission element is known. These electron emission elements are electron emission-emitting elements that emit electrons from the surface of the planar element by utilizing the quantum size effect inside the element and a strong electric field to accelerate electrons. The electronic emitting elements release the accelerated electrons inside the element, so that no strong electric field is required outside the element, so the above-mentioned Spindt type & CNT type and BN type electronic emitting elements can be overcome in the MIM type and MIS type electronic emitting elements. A problem of damage due to riding caused by ionization of gas molecules, or a problem of ozone generation. The electron emission member of the above-mentioned picture is proposed as an electron-emitting element using a porous semiconductor formed by anodization of a semiconductor (for example, multi-cut), and an electron is injected into the porous semiconductor at an electric field. The medium is accelerated 'and the electrons are passed through the surface metal by a wear-through effect, and the film is released in a vacuum (for example, refer to Patent Document 2). Further, the electron-emitting element of the t-hole semiconductor has a large advantage in that the element can be manufactured by the extremely simple and inexpensive manufacturing method of % pole oxidation. In addition, there is known an electron emission element which is formed by overlying a layer of 136193.doc 200947492 semiconductor fine particles or metal fine particles covered with an insulating layer (for example, refer to Patent Document 3). [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 3] Japanese Laid-Open Patent Publication No. Hei 9-9499 (published on January 1, 1997) ^ [Non-Patent Document 1] Yamaguchi and other three persons "Photograph of using carbon nanotubes" Development of a high-efficiency electron beam source for recording", Japan Hardc〇py97 Proceedings, 曰本本像学会, July 1997, P221-224 [Summary] However, when making the above-mentioned electronic of MIM type or MIS type When the emitting element operates in the atmosphere, there is a new problem that various gas molecules are adsorbed on the surface of the element, thereby deteriorating the electrical characteristics of the semiconductor, and reducing the current discharged by the electron. In particular, the formation of a large problem that semiconductor oxidation degradation due to oxygen in the atmosphere cannot be avoided. The surface of the MIM-type or MIS-type prior electronic discharge element that accelerates electrons inside the elements is responsible for applying an electric field upper electrode to the inside of the element, and is generally composed of a metal thin film. Moreover, the surface of the previous electronic discharge element of the MIM type or the MIS type is also responsible for the electron tunneling of the metal film which is accelerated inside the element and is discharged into the vacuum. The thinner the film thickness of the metal film, the acceleration of the inside of the element The higher the random wear rate of the electrons, and the more the electron emission amount. Therefore, it is preferable that the film thickness of the thin metal 136193.doc 200947492 is thinner. However, if the film thickness of the metal thin film is excessively thin, it is difficult to form a dense film, and the barrier effect against gas molecules is almost eliminated. Therefore, when the electron emission element is operated in the atmosphere, there arises a problem that gas molecules intrude into the inner semiconductor layer, so that the electrical characteristics of the semiconductor are changed and the electron emission current is reduced. As a result, in an electron emission element obtained by repeatedly depositing fine particles of semiconductor fine particles or metal fine particles and covering the outer side with the insulating layer t, it is impossible to stably generate electrons in the atmosphere, particularly when the insulating layer is When the semiconductor fine particles or the oxide film of the metal fine particles are formed, oxygen in the atmosphere promotes oxidation of the fine particles, thereby causing an increase in the film thickness of the oxide film. An increase in the film thickness of the oxide film causes a decrease in the electron tunneling rate, which eventually causes the electron emission to stop. On the other hand, the insulating film having a film thickness of electron tunneling has a low resistance value, and when excessive current flows in the element, dielectric breakdown or heat generation occurs, thereby causing the following problem: Damage caused by the insulating ❹ layer causes the component to be damaged. The present invention is accomplished by the above problems, and the object of the present invention is to provide an electron which can emit stable electrons not only in a vacuum but also at atmospheric pressure, and can suppress generation of harmful substances such as ozone or bismuth (伴随) accompanying electron emission. Release components and the like. In order to solve the above problems, the electron emission device of the present invention is characterized in that it has an electrode substrate and a thin film electrode, and electrons are applied between the electrode substrate and the thin film electrode to cause electrons between the electrode substrate and the thin film electrode. Accelerating 'the electrons are emitted from the thin film electrode, and an electron accelerating layer is formed between the electrode substrate I36I93.doc 200947492 and the electrode. The electron accelerating layer package and the electric conductor are formed and the oxidation resistance is high. The microparticles and the insulator material having a larger size than the above-mentioned conductive microparticles. According to the above configuration, an electron addition layer is provided between the electrode substrate and the thin film electrode. The electron acceleration layer includes a conductive material having a high oxidation resistance and a larger size than the conductive fine particles. The insulator y here has a high oxidation resistance, which means that the oxide formation reaction is low. The amount of change in the free energy of oxide formation obtained by the table & general thermodynamic leaf calculation ΔG [U/mol] value is greater negative. The more likely it is to cause an oxide formation reaction. In the present invention, the metal element corresponding to Δ~(iv) [kJ/m〇_ is suitable as the conductive fine particles having high oxidation resistance. Further, the conductive fine particles in a state in which an insulator substance smaller than the size of the conductive fine particles is attached or coated around a suitable conductive fine particle and is more difficult to cause an oxide formation reaction is also contained in the conductive fine particle having high oxidation resistance. . The electron-accelerating layer-based insulator material and the conductive particles having high oxidation resistance are layered with a thin layer of σ, and have semiconductivity. When a voltage is applied to the semiconducting electron acceleration layer, a current flows in the electron acceleration layer, and a part thereof is released as a ballistic electron by a strong electric field formed by applying a voltage. Further, since a conductor having a high oxidation resistance is used as the conductive fine particles, it is difficult to cause oxidation due to oxidation by oxygen in the atmosphere, and the element can be deteriorated. Therefore, it is possible to stably operate at atmospheric pressure. Further, since the insulator substance and the conductive fine particles can adjust the resistance value and the amount of generated ballistic electrons in the electron acceleration layer, it is possible to control the current value and the electron emission amount flowing in the acceleration layer of the electron 136193.doc -10- 200947492. Further, the insulator may have a function of efficiently releasing Joule heat generated by a current flowing in the electron acceleration layer, so that the electron emission element can be prevented from being thermally damaged. The electronic discharge element of the present invention has the above-described configuration, so that it is not accompanied by a discharge in a vacuum or in an atmospheric pressure, so that harmful substances such as ozone or helium are hardly generated, and the electron emission element is not oxidized and deteriorated. Therefore, the electronic discharge element of the present invention has a long life and is continuously operated in the atmosphere for a long time. Therefore, according to the present invention, it is possible to provide an electron emission element which can stably emit electrons not only in a vacuum but also under atmospheric pressure, and which suppresses generation of harmful substances such as ozone or helium. Other objects, features, and advantages of the present invention will be apparent from the description of the appended claims. Further, the benefits of the present invention will be apparent from the following description with reference to the accompanying drawings. [Embodiment] Hereinafter, an embodiment of an electronic discharge device according to the present invention will be specifically described with reference to Figs. 1 to 17 . Further, the embodiment I and the examples described below are only specific examples of the present invention, and the present invention is not limited by the embodiments and examples. [Embodiment 1] Fig. 1 is a schematic view showing a configuration of an embodiment of an electron emitting element of the present invention. As shown in Fig. 1, the electron emission element 1 of the present embodiment includes a substrate (electrode substrate) 2 as a lower electrode, an upper electrode (thin film electrode) 3, and a substrate (electrode substrate) 2 and an upper electrode (film). Electron acceleration layer 4 between electrodes 3 . Further, both the substrate 2 and the upper electrode 3 are connected to 136193.doc 200947492: source #, and electric waste can be applied to the substrate 2 and the upper electrode 3 which are disposed to face each other. The electron emission element 1 causes a current to flow between the substrate 2 and the upper electrode 3, that is, the electron acceleration layer 4, by applying a voltage between the substrate 2 and the upper electrode 3, and a boring tool forms a strong electric field of applied voltage. It acts as ballistic electrons and penetrates the upper electrode 3 or is released from the gap of the upper electrode 3. Going again, ± φ 2 , the electron emission device 1 and the power source 7 form an electron emission device"

The substrate 2 as the lower electrode is responsible for the support of the electron emission element. Therefore, it is not particularly limited as long as it has good adhesion to a material having a certain degree of strength and is in direct contact with the material, and has appropriate conductivity. For example, a metal substrate such as sus or Ti or Cu; a semiconductor substrate such as Si or Ge or a shirt; an insulator substrate such as a glass substrate; and a plastic substrate can be cited. When an insulator substrate such as a glass substrate is used, a conductive material such as metal adheres to the interface between the electron acceleration layer 4 and the electron acceleration layer 4, and the insulator substrate can be used as the substrate 2 serving as the lower electrode. As the conductive material f, a noble metal-based material having excellent conductivity can be formed into a thin film by a method such as a magnetic control, and the constituent material is not particularly problematic. Moreover, as an oxide conductive material, an IT0 film widely used in a transparent electrode is also useful. Further, in terms of forming a tough film, for example, a Ti film having 2 Å (10) formed on the surface of a glass substrate, and a metal film having a film of 1 Å formed thereon may be formed. It is not limited to the above materials and numerical values. The upper electrode 3 is a person who applies a voltage to the electron acceleration layer 4. Therefore, as long as the material for applying a voltage to the month b can be used, it is not particularly limited. However, from the viewpoint that the electrons in the electron acceleration layer 4 which are accelerated to reach high energy are penetrated as far as possible without energy consumption, as long as the work function is low and the shape is = the material of the film, You can expect higher results. Examples of such a material include gold, silver, carbon, tungsten, titanium, aluminum, palladium, and the like having a work function equivalent to 4 to 5 eV. Among them, in the case where the operation in the atmospheric pressure is set, the gold which is not formed by the oxidation of the substance and the sulfide is the optimum material. In addition, the oxide formation reaction is relatively small, such as silver, palladium, tungsten, etc., which is also a practical material and has a problem. The film thickness of the upper electrode 3 is more important, and it is used as a self-electron emission element. 1 The conditions for efficient emission to the outside are preferably in the range of 10 to 55 nm. The upper electrode 3 is used as a planar electrode: the minimum film thickness is 10 nm, and the thickness of the thickness is not sufficient to ensure electrical conduction. On the other hand, the maximum film thickness for ejecting electrons from the electron emitting element to the outside is 55 nm, beyond which the ballistic electrons cannot be penetrated, and on the upper electrode 3, absorption due to ballistic electrons may occur. Re-capture of the electron acceleration layer 4 by reflection. The 子t sub-acceleration layer 4 may contain conductive microparticles formed of a conductor and having high oxidation resistance, and an insulator material having a larger size than the above-mentioned conductive microparticles. In the present embodiment, the conductive fine particles are described as the metal fine particles 6. Further, in the present embodiment, the insulator material is described as fine particles 5 having an average diameter larger than the average diameter of the metal fine particles 6, i.e., fine particles 5 of the insulator. However, the configuration of the electron acceleration layer 4 is not limited to the above, and the insulator may be formed as a layer on the substrate 2 and have a plurality of openings penetrating through the thickness direction of the layer, and Conductive fine particles are accommodated in the opening. 136193.doc • 13- 200947492 In the present embodiment, the electron acceleration layer 4 contains the fine particles 5 and the metal fine particles 6 of the insulator. Therefore, the electron acceleration layer 4 is hereinafter referred to as the fine particle layer 4. Here, as the metal species of the metal fine particles 6, an arbitrary metal species β can be used from the principle of generating ballistic electrons. However, in order to avoid oxidative degradation during operation at atmospheric pressure, it is necessary to use a metal having high oxidation resistance. The noble metal is preferably a material such as gold, silver, platinum, palladium or the like. Such metal fine particles 6 can be produced by a well-known fine particle manufacturing technique, that is, a ship method or a spray heating method, or a commercially available metal fine particle powder such as silver nanoparticle produced by Nano Research. The principle of generation of ballistic electrons is described below. Here, since it is necessary to control the conductivity, the average diameter of the metal fine particles 6 must be smaller than the size of the fine particles 5 of the insulator described below, more preferably 3 to 10 nm. As described above, the average diameter of the metal fine particles 6 is smaller than the particle diameter of the fine particles 5 of the insulator, and is preferably set to 3 to 1 〇 nm, whereby the conductive of the metal fine particles 6 is not formed in the fine particle φ sub-layer 4. The passage is difficult to cause dielectric breakdown in the fine particle layer 4. Further, in principle, there are many ambiguities, but ballistic electrons are efficiently generated by using the metal fine particles 6 having the particle diameter within the above range. Further, 'the periphery of the metal fine particles 6' may also have an insulator material smaller than the size of the metal fine particles 6, and the insulator material having a smaller size than the metal fine particles 6 may be attached to the surface of the metal fine particles 6. The substance and the adhering substance may be an insulating film which is a surface of the metal fine particles 6 which is coated with the metal fine particles 6 as an aggregate having a smaller average diameter than the metal fine particles 6 136193.doc -14·200947492. As the insulator material having a smaller size than the metal fine particles 6, an arbitrary insulator material can be used from the principle of action of generating ballistic electrons. However, the insulating material having a size smaller than that of the metal fine particles 6 is an insulating film covering the metal fine particles 6 'when an insulating film is provided according to the oxide film of the metal fine particles 6, ' may be oxidized due to oxidative degradation in the atmosphere. In order to avoid oxidative degradation during operation at atmospheric pressure, it is preferable that the insulating film formed of an organic material is, for example, an alcoholate, a fatty acid, a burned mercaptan, or the like. material. It is advantageous to use a thinner thickness of the insulating film. The fine particles 5 of the insulator can be used as long as they have insulating properties, and are not particularly limited. However, as shown in the experimental results described below, the weight ratio of the fine particles 5 of the insulator among all the fine particles constituting the fine particle layer 4 is 80 to 95%, and in order to obtain a more excellent heat dissipation effect with respect to the metal fine particles 6, the fine particles of the insulator The size of 5 is preferably larger than the diameter of the metal fine particles 6, and the diameter (average diameter) of the fine particles 5 of the insulator is preferably 10 to i_nm, more preferably 12 to 11 Å (10). Therefore, Si 〇 2, Μ " 3, Ti 〇 2 in the material of the fine particles 5 of the insulator are practical. However, when the surface-treated small-sized cerium particles are used, the surface area of the cerium particles in the solvent is increased and the viscosity of the solution is increased as compared with the case of using the spheroidal cerium particles having a larger particle diameter. Therefore, the film thickness of the fine particle layer 4 tends to increase slightly. Further, as the material of the fine particles 5 of the insulator, fine particles formed of an organic polymer, for example, highly crosslinked fine particles (SX8743) formed of styrene/divinyl styrene which can be manufactured and sold by JSR Co., Ltd., or Japan Paint Co., Ltd. 136193.doc 200947492 Division (NIPPONPAINT Co., Ltd.) manufactures and sells the Fine Sphere series of styrene-acrylic microparticles. Here, as the fine particles 5 of the insulator, two or more different particles may be used, and particles having different peak diameters may be used, or a single particle may be used and the particle size distribution may be wide. Further, since the action of forming the insulator does not depend on the shape of the fine particles, the insulator material may be a sheet substrate made of an organic polymer or an insulator layer formed by applying an insulator material by an arbitrary method. However, the sheet substrate or the insulator layer must have a plurality of micropores penetrating through the thickness ❹. As a sheet-like base material satisfying such a condition, for example, a membrane filter Nuclepore® (made of polycarbonate) manufactured by Whatman Japan Co., Ltd. is used. The thinner the microparticle layer 4 is, the stronger the electric field is generated. Therefore, electrons can be accelerated by applying a low voltage. However, the electron acceleration layer can be made uniform in thickness and the electron acceleration layer in the layer thickness direction can be formed. The layer thickness of the fine particle layer 4 is preferably from 12 to 6 nm, more preferably from 300 to 6000 nm.继 Next, explain the principle of electronic emission. Fig. 2 is a schematic enlarged view showing a cross section of the vicinity of the fine particle layer 4 of the electron-emitting member 1. As shown in Fig. 2, most of the fine particle layer 4 is composed of fine particles 5 of an insulator, and metal fine particles 6 are scattered in the gap. The ratio of the fine particles 5 and the fine metal particles 6 of the insulator in Fig. 2 is a state corresponding to the ratio of the weight of the fine particles 5 of the insulator to the total weight of the fine particles 5 and the fine metal particles 6 of the insulator of 8 〇. %, and the metal fine particles 6 attached to each of the particles of the insulating fine particles 5 are about six particles. 136193.doc -16- 200947492 ❹

The microparticle layer 4 is composed of the fine particles 5 of the insulator and a small amount of the metal fine particles 6, and thus has semiconductivity. Therefore, when a voltage is applied to the fine particle layer 4, an extremely weak current flows. The voltage-current characteristic of the microparticle layer 4 shows a so-called varistor characteristic, and the current value rapidly increases as the applied voltage rises. One of the currents becomes a ballistic electron under the action of a strong electric field in the fine particle layer 4 formed by applying a voltage, and passes through the upper electrode 3 or is discharged to the outside of the electron emission element through the gap. Regarding the formation process of the ballistic electrons, it is considered that the electrons are accelerated in one direction in the direction of the electric field, but it cannot be determined. Next, an embodiment of a method of generating the electron emission element 1 will be described. First, a dispersion solution of the fine particles 5 and the fine metal particles 6 in which the insulator is dispersed is applied onto the substrate 2 by spin coating to form the fine particle layer 4. Here, the solvent to be used in the dispersion solution is not particularly limited as long as it can disperse the fine particles of the insulator + 5 and the fine metal particles 6 and can be dried after coating, and for example, toluene, benzene, xylene, or the like can be used. Hexane, tetradecane, and the like. Further, in order to improve the dispersibility of the metal fine particles 6, an alcoholate treatment may be carried out as a pretreatment. The film thickness of the film can be formed by repeating the film formation and drying treatment of the spin coating method. Microparticle Layer In addition to the spin coating method, a film can be formed by a method such as a dropping method, and the upper electrode 3 is formed on the electron acceleration layer 4. When the upper electrode 3 is formed into a film, for example, a magnetron-killing method can be used. In the electron emission element 1, when an insulator substance (corresponding to the fine particles 5 of the insulator on the fine particle layer 4) on the electron acceleration layer forms an insulating material of the layer, it can be produced as follows. First, on the substrate 2, 136193.doc 17 200947492, an insulator material (hereinafter referred to as a sheet-like insulator material) having a plurality of openings extending in the thickness direction of the layer is laminated or coated on the substrate 2. The coating liquid of the insulator substance is dissolved/dispersed to form an insulator layer. For the sheet-like insulator material, for example, a sheet-like substrate composed of an organic polymer, Si〇2, and barium oxide can be used. For the material forming the insulator layer, SiO 2 , ai 2 o 3 , and Ti 〇 2 or organic polymerization can be used. Things.

Here, as for the plurality of openings, as long as the organic polymer is used, it may be formed by a punching method using a blade or a laser drilling method using high-energy laser irradiation, and the like. For the substance consisting of si〇2, gossip 2〇3, an anodizing method, in particular, a nanoporous material for forming Si〇2, a hydrothermal reaction method using a surfactant as a mold, or the like can be used. To form the desired opening. Further, it must be more than the diameter of the metal fine particles used, and preferably 5 〇 50 50 (10). A plurality of openings are formed in an insulator layer formed by laminating a sheet-like insulator material having such an opening on the substrate 2 or applying a coating liquid in which an insulator substance is dissolved/dispersed. Here, in the above description, the substrate 2 is laminated with a sheet-like insulator material having an opening portion, but an opening portion may be formed on the sheet-like insulator material after the substrate 2 is laminated with a sheet-like insulator material. . Thereafter, the opening of the sheet-like insulator material * ^ . s 〇 〇P is filled with the metal fine particles 6 covered with the insulating film. At this time, for example, ^ ^ . s , 1 The solution of the metal microparticles 6 is oozing &, ^ is left to the opening and is naturally dried, thereby forming the electron accelerating layer 4. Then, the sentence is tempered and the π < The coated metal fine particles 6 are dispersed in a solvent, but are directly infiltrated into the opening by air blowing, suction, 136193.doc -18-200947492, or grinding, etc. Next, the upper electrode 3 is formed in the above-described manner. When the upper electrode 3 is formed into a film, for example, a magnetron sputtering method can be used. (Example 1) An electron emission experiment using the electron emission device of the present invention as an embodiment is shown in FIG. Further, the experiment is merely an example of implementation, and is not intended to limit the scope of the present invention. Ο ❹ In this embodiment, fine particles 5 of an insulator on the fine particle layer 4 are formed, and an insulator is attached to the surface. Substance Five kinds of electron emission elements 1 whose composition of metal fine particles 6 were changed. As the substrate 2, a SUS substrate of 3 mm square was used, and the fine particle layer 4 was deposited on the substrate 2 by spin coating. In the method, the fine particles 5 containing the insulator and the metal fine particles 6 on the surface of which the insulator is adhered are dispersed in various kinds of particles using toluene as a solvent. The fine particles 5 of the insulator dispersed in the toluene/mixture adhere to the surface. In the composition ratio of the metal fine particles 6 having an insulator substance, the weight ratio of the fine particles 5 of the insulator is 70%, 80%, 90%, 95% with respect to the total amount of the fine particles $ and the metal fine particles 6 of the insulator. As the metal fine particles 6 to which an insulator substance is attached, silver nano particles are used (average diameter A 10 nm, in which the thickness of the insulating film alkoxide is 1 particle microparticle 5, and the money is (4) germanium particle (; the average diameter is 110 Nrn). A solution in which various fine particles are dispersed is prepared in the following manner: 3 toluene solvent is poured into a U) mL reagent bottle, and 〇5 g of shi 136193.do is poured thereinto. c 200947492 Particles. Here, the reagent bottle is placed on an ultrasonic disperser to disperse the ruthenium particles. Thereafter, 0.055 g of silver nanoparticles are additionally charged, and ultrasonic dispersion treatment is performed in the same manner. The composition ratio of the ruthenium particles is 90% dispersion solution. The film formation conditions of the spin coating method are such that after the dispersion solution is dropped onto the substrate, the substrate is rotated at a speed of 500 RPM for 5 sec, followed by 3 〇〇〇 RpM. The rotation was performed for 10 sec. The film formation conditions were repeated 3 times on the substrate and then dried naturally at room temperature. The film thickness is about 〇〇5〇〇 nm. After the fine particle layer 4 is formed on the surface of the substrate 2, the upper electrode 3 is formed into a film by a magnetron sputtering apparatus. Using gold as the tantalum material, the upper electrode 3 has a layer thickness of 12 nm' and an area of 0.28 cm2. For the electron emission element fabricated in the above manner, an electron emission experiment was performed using the measurement system shown in Fig. 3. In the experimental system of FIG. 3, on the upper electrode 3 side of the electron emission element 1, the insulator spacer 9 is sandwiched and the counter electrode 8» is disposed, and the electron emission element 丨 and the counter electrode 8 are connected to the power source. 7', a voltage vi is applied to the electron emission element 1, and a voltage ν2β is applied to the counter electrode 8. The experimental system is placed in a vacuum of ΐχΐ〇_8 ATM to perform an electron emission experiment, and further, the experimental system is It was placed in the atmosphere and subjected to an electron emission experiment. The experimental results of these are shown in Figures 4 to 7. Fig. 4 is a graph showing the results of measurement of electron emission current when an electron emission experiment is performed in a vacuum. Here, let Vl = l~10 V and V2 = 50 V. As shown in Fig. 4, in the vacuum of 1x1 〇_8 ATM, no electron emission is observed when the weight ratio of cerium particles is 70%. In contrast, when the ratio is I36193.doc -20- 200947492 80%, At 90% and 95 〇/0, currents due to electron emission were observed. This current value is about 丨〇7 A when the voltage of i 0 V is applied.囷5 is a graph showing the measurement results of the current in the element when the electron emission test was performed in a vacuum in the same manner as described above. Here again, the same as above, such that V1MM0 v, V2 = 5 〇 v. According to Fig. 5, when the ratio of the ruthenium particles is 70%, the resistance value is insufficient, causing dielectric breakdown (the current value is abnormal and is closely attached to the upper portion of the graph). If the composition ratio of the metal fine particles is increased, it is easy to form a conductive path of the metal fine particles, and the fine particle layer 4 will have a low voltage and a large current will flow. Therefore, it is considered that the conditions for the production of ballistic electrons are not established. 6 is a graph showing the results of measurement of the electron emission current and the current in the element when an electron emission experiment is performed in the atmosphere when Vl = 1 to 15 V and V2 = 200 V using an electron emission element having a ratio of ruthenium particles of 9 %. Chart. As shown in Fig. 6, a voltage of V1 = 15 v was applied to the atmosphere, whereby a current of about 10_1 ί) was observed. Further, Fig. 7 shows an electron emission current when the ratio of the ruthenium particles is 9 〇% in the same manner as in Fig. 6 and the voltage is continuously driven in the atmosphere with an applied voltage of V1 = 15 v and V2 = 200 V. And a graph of the measurement results of the current in the component. As shown in Fig. 7, the current is continuously and stably discharged even after a lapse of 6 hours. (Embodiment 2) In the present embodiment, the following four electron emission elements 1 are produced: the composition of the fine particles 5 of the insulator on the fine particle layer 4 and the metal fine particles 6 to which the insulator is adhered on the surface is the same as in the above-described first embodiment, However, the film formation conditions of the fine particle layer 4 are changed, and the layer thickness thereof is changed. 136193.doc 21 200947492 The composition ratio of the fine particles 5 of the insulator dispersed in the dispersion solution used for spin coating to the metal fine particles 6 having the insulator substance adhered to the surface is adjusted to be the total input with respect to the fine particles 5 and the fine metal particles 6 of the insulator. The amount of the fine particles 5 of the insulator was 80% by weight, and the film forming conditions of the spin coating method were carried out once or five times. Further, in the film forming conditions of the spin coating method, the amount of the coating liquid supplied to the coated surface was reduced, and this was also carried out under the conditions of the first spin coating. Further, the prior film forming method is different, and the film formation of the fine particle layer 4 is also carried out by a method of dropping only the dispersion solution onto the surface of the substrate 2. The relationship between each film forming condition and the layer thickness of the fine particle layer 4 is shown in Table 1. [Table 1] _ Film formation conditions The thickness of the coating layer of the fine particle layer 4 is applied once by spin coating, once by spin coating, 300 nm, 780 nm, sub-spin coating, 3000 nm, one drop of 6000 nm, 2 drops, --- 19000 Nm uses the measurement system shown in Figure 3 to determine the electricity produced in this embodiment.

The measurement result of the discharge element 1' is as follows. When V1 = 1~2 〇v, V2=5 0 V, it can be seen that in the vacuum of lxl〇-8 ATM, the layer thickness of the fine particle layer 4 is between 3 〇〇 nm and 6 〇〇 () nm. The electronic emission element in the range has an electron emission 'relative to this'. The element in the electron emission element having a layer thickness of 19,000 nm has a high resistance, so that a sufficient current cannot flow in the element, and electron emission is not performed. L36193.d〇, 2222, and 200947492 (Example 3) In the above Examples 1 and 2, spherical cerium particles in which fine particles 5 as insulators are dispersed in a toluene solvent, and metal fine particles to which an insulator substance is attached as a surface are dispersed. A system of silver nanoparticles coated with an alkoxide film. In the present embodiment, gold, platinum and palladium were used as the metal fine particles to form an electron emission element. Since the film formation method of the microparticle layer 4 was carried out by the above-described spin coating method, a solution in which the respective fine particles were dispersed was formed in the following manner. Pour 3 mL of ethanol solvent into a 10 mLi bottle, and add 5 g of globular Shixia particles (average diameter is 110 nmp here, place the reagent bottle on the ultrasonic disperser). The particles are dispersed. Then, 55 g of gold fine particles (average particle diameter of 3 nm) are additionally charged, and ultrasonic dispersion treatment is also performed. Under this condition, relative to the total weight of the fine particles in the dispersion solution The composition ratio of the ruthenium particles is 90%. The conditions of the spin coating method are the same as those of the above embodiment, but the hydrophilization treatment using a decane coupling agent must be carried out on the surface of the sus β 2 substrate as a pretreatment. On the surface of the fine particle layer 4 thus formed, the upper electrode 3 was formed by using a magnetron killing device, and gold was used as a film forming material, and the layer thickness of the upper electrode 3 was 12 nm, and the area was 〇28 cm2. The electron emission element was in a vacuum of lxl〇-8 ATM, and when an applied voltage to the upper electrode was 10 V, an electron emission current of 6 x 1 〇-8 A was observed. It was also confirmed that for the platinum fine particles and the palladium microparticles, By the same The electron emission element can be produced by the production method, and electron emission can be performed. 136193.doc -23- 200947492 (Embodiment 4) In the present embodiment, fine particles formed of an organic polymer are used as the fine particles 5 of the insulator of the fine particle layer 40. The electron discharge element was produced. As in the previous embodiment, the film formation method of the fine particle layer 4 was carried out by the above-described spin coating method, so that a solution in which various fine particles were dispersed was prepared as follows. 3 mL of the toluene solvent was poured into 1 〇mL. In the reagent bottle, the highly crosslinked polymer microparticles (SX8743: average diameter: 50 nm) manufactured by JSR Co., Ltd., which is 0·5 g, are put into the reagent bottle. Here, the reagent bottle is placed on the ultrasonic disperser. The dispersion of the highly crosslinked polymer microparticles was followed by the addition of 0.055 g of silver nanoparticles prepared by the application of the Nano Research Institute, and the ultrasonic dispersion treatment was carried out in the same manner to obtain a microparticle dispersion solution. Similarly to the above, the film formation is repeated three times on the surface of the substrate 2 of sus, whereby the fine particle layer 4 having a film thickness of about 1 〇〇〇 nm can be obtained. On the surface of the layer 4, a portion of the upper electrode 3 having a thickness of 40 nm was formed using a gold material to form an electron emission element. It was confirmed that the electron emission element of the present embodiment also had electron emission. (Embodiment 5) In this embodiment, A sheet-like substrate formed of an organic polymer is used as an insulator substance in the electron acceleration layer (corresponding to the fine particles 5 of the insulator on the fine particle layer 4 in the above embodiments 丨 to 4) to fabricate an electron emission element.

On the substrate 2, the opening portion 5 1 C is out of the electron acceleration layer 4 of the 1 〇 1 ′, and the cross section in the vicinity is placed in the embodiment. The insulator material 5 is in the form of a sheet and the layer is formed to have a plurality of layers penetrating the layer. The shape of the opening portion 51 136193.doc •24· 200947492. As the substrate 2', a 30 mm square SUS substrate was used, and a polycarbamate sheet having a thickness of 6 μm was laminated thereon as the insulator material 5. Further, on the polycarbonate sheet, an opening portion (hole) 5 1 ' of φ 5 〇 nm was opened at a ratio of six per i 01112, and the aperture ratio was about 1.2%. The opening 5 丨 passes through the lamination direction of the sheet. Then, it will act as metal fine particles 6 with an insulator substance attached to the surface.

The gold nanoparticles (average particle size 〖〇 nm, in which the water-soluble high molecular weight of the insulating film is 1 nm) are dispersed in water as a solvent at a concentration of 2.5 mmol/L. The solution was dropped into a sheet of the above polycarbonate in an appropriate amount, and allowed to permeate into the opening portion 51, and then allowed to dry naturally. The upper electrode 3 is made of gold and has a layer thickness of 12 nm* deposited by magnetron sputtering on a sheet of polycarbonate in which gold nanoparticles are embedded in the opening 51 (electron acceleration layer state. The electrode area is 0.28 cm2. With respect to the electron emission device produced by the above method, it was confirmed by the measurement system shown in Fig. 3 that an electric current was generated by the electron emission test. Further, in the present embodiment, The metal fine particles 6 having the insulator substance adhered to the surface thereof are allowed to permeate into the opening portion 51 by dropping the solution, but the metal fine particles 6 may be directly infiltrated by means of air blowing, suction, or polishing without dispersing the metal fine particles 6 in a solvent. [Embodiment 2] The electronic discharge of the present invention is as follows. The charging device 90 includes an electro-mechanical device 9 showing an example of the charging device 9 of the present invention using the element 1 of the first embodiment. 136193.doc -25-200947492 sub-emission element 1 and a power source 7 to which a voltage is applied, and the photoreceptor "charger" includes the charging device 9 of the image forming apparatus of the present invention. In the image forming apparatus of the present invention, the composition The electron emitting element 1 of the electric device 90 is disposed opposite to the photoreceptor 11 as a charged body, and emits electrons by applying a voltage to charge the photoconductor 11, and in addition, the image forming apparatus of the present invention is charged. The constituent members other than the device 90 may be used as long as it is known. Here, the electron emitting element 1 used as the charging device 9 is preferably disposed so as to be separated from the photoconductor 11 by, for example, 3 to 5 mm. The applied voltage to the electron emission element 1 is preferably about 25 V, and the electron acceleration layer of the electron emission element 1 can be configured such that, for example, when a voltage of 25 V is applied, 1 yA/cm 2 is released per unit time. The electron emission element 1 used as the charging device 90 is not accompanied by discharge even when operating in the atmosphere, so that ozone is not generated from the charging device 90 at all. Ozone is harmful to the human body and is limited to various environments. Within the specification, φ is not, even if the ozone is not released to the outside of the device, the organic material inside the device, such as the photoreceptor 11 or the belt, may be oxidatively degraded. The problem can be solved by the following method: The electronic discharge element 1 of the present invention is used for the charging device 90, and the charging device 90 has an image forming apparatus. Further, the electronic discharging element used as the charging device 90 is configured. Since it is a surface electron source, the photoreceptor 11 is also charged in a certain range in the rotation direction, so that a motor of a certain portion of the photoreceptor can be obtained in a large amount. Therefore, with a wire-shaped and charged wire charger, etc. In contrast, the charging device 9〇 can evenly radiate 136193.doc •26·200947492. And 'the charging device 90 also has a very low voltage of about 1 〇V compared to a corona discharger that requires a voltage of several kv. Advantages of Voltage: [Embodiment 3] An example of the electron beam curing apparatus 100 of the present invention using the electron emitting element 1 of the present invention described in the first embodiment is shown in Fig. 10. The electron beam hardening device 1 includes an electron emission element 1 and a power source 7 for applying a voltage thereto, and an acceleration electrode 21 for accelerating electrons. In the electron beam curing apparatus 1A, the electron emission element 1 is used as an electron source, and the emitted electrons are accelerated by the acceleration electrode 21 to collide with the photoresist 22. In order to harden the general photoresist 22, the energy required for curing is 1 〇 or less. Therefore, if only the energy can be set, it is not necessary to accelerate the electrode. However, the penetration depth of the electron beam becomes a function of the energy of the electron, and therefore, an acceleration voltage of about 5 kV is required when, for example, all of the photoresist 22 having a thickness of i μη is hardened. In a general electron beam hardening apparatus which has been used in the prior art, the electron source is vacuum-sealed, electrons are emitted by applying a high voltage (5 〇 to 1 〇〇 kv), and electrons are taken out through the electron holes to be irradiated. If the method of electron emission is employed, a large energy loss occurs when penetrating the electron hole. Moreover, since the electrons reaching the photoresist also have high energy, the thickness of the photoresist can be worn, resulting in a decrease in energy utilization efficiency. Further, the range in which the irradiation is possible is narrow, and the spotting is performed in a dot shape, so the amount of processing is also low. On the other hand, the electron beam curing device of the present invention using the electron emitting element 1 of the present invention can be operated in the atmosphere, so that it is not necessary to perform vacuum sealing. Moreover, there is no loss of energy because it does not pass through the electron penetration hole, so that the applied voltage can be reduced by 136193.doc •27-200947492. Furthermore, due to the surface electron source, the amount of processing is very high. Further, if the electrons are emitted according to the pattern, the maskless exposure can be performed. [Embodiment 4] An example of a self-luminous device of the present invention using the electron emission element 1 of the present invention described in Embodiment 1 is shown in Figs. 11 to 13 respectively. The self-luminous device 31 shown in FIG. 11 includes an electron emission element 1 and a power source 7 for applying a voltage thereto, and a light-emitting portion 36 which is located at a position separated from and opposite to the electron emission element 1 and has a substrate as a substrate. The laminated structure of the glass substrate 34, the ITO film 33, and the phosphor 32. As the phosphor 32, an electrophotographic material corresponding to red, green, and blue luminescence is suitable, e.g., in the case of red, Y2〇3 : , (γ,

Gd) B03 : Eu ; in terms of green, Zn2Si〇4 : Mn, BaAl12〇19 : Μη; in terms of blue, BaMgAli〇〇i7 : Eu2+ can be used to form a glass substrate with an ITO film 33 On the surface of 34, the glory body 32 is formed into a film. The thickness of the phosphor 32 is better! Ιιη or so. Further, the film thickness of the IT film 33 is as long as it is a film thickness which can ensure conductivity, and is 150 nm in the present embodiment. When the phosphor 32 is formed into a film, a kneaded material of an epoxy resin as a binder and fine particles of the phosphor particles can be prepared, and a film can be formed by a known method such as a bar coating method or a dropping method. Here, in order to increase the luminance of the light-emitting body 32, it is necessary to accelerate the electrons emitted from the electron emission element 1 toward the phosphor. In this case, the ITO of the substrate 2 and the light-emitting portion 36 of the electron emission element 1 Between the membranes 33, a power supply 35 can be provided for the application 136193.doc • 28- 200947492. The distance between the elements 1 is V. From the voltage applied by the power source 35 to form an electric field for accelerating electrons, it is preferable that the phosphor 32 and the electrons emit 0.3 to 1 mm, and the applied voltage from the power source 7 is applied. Apply a voltage of 18 to 500~2000 V »

The self-luminous device 31 shown in Fig. 12 is provided with a power source 7 for applying a voltage to the electron emitting element i, and a phosphor 32. In the self-luminous device 31, the polishing body 32 is planar, and the phosphor 32 is disposed on the surface of the electron emitting element i. Here's for the electronic release component! As described above, the layer of the light-emitting body 32 formed on the surface of the film is formed into a film on the surface of the electron emission element 1 by preparing a coating liquid formed of a kneaded material with the fine-grained glazing particles. However, since the structure of the electron emission element itself is weak with respect to the external force, it may cause destruction of the element when the film formation method by the bar coating method is used. Therefore, a method such as a dropping method or a spin coating method can be used. The self-luminous device 31" shown in Fig. 13 is provided with an electron emission element 丨 and a power source 7 to which a voltage is applied, and further, fine particles of fluorescence are mixed in the fine particle layer hopper of the electron emission element 作为 as a glare body 32'. At this time, the fine particles of the glare body 32' can also be used as the fine particles $ of the insulator. However, in general, the above-mentioned phosphor particles have a low electric resistance, and the electric resistance is remarkably low as compared with the fine particles 5 of the insulator. Therefore, when the fine particles of the phosphor are changed to the fine particles 5 of the insulator and mixed, it is necessary to control the amount of the fine particles of the phosphor to be small. For example, when spheroidal ruthenium particles (average diameter 11 〇 nm) are used as the fine particles 5 of the insulator, and ZnS: Mg (average diameter 500 nm) is used as the phosphor granules, the weight mixing ratio is about 3:1. . The self-luminous devices 31, 31, 31, 'the electrons emitted from the electron emission element 1 are 136193.doc • 29· 200947492, and the electrons collide with the phosphors 32 and 32 to emit light. Furthermore, in the 'self-luminous devices 31, 31', 31'', the 'electronic emission element 1 can emit electrons in the atmosphere', so that it can operate in the atmosphere. However, if it is vacuum-sealed, the electron emission current will rise, and thus the current can be increased. Efficiently emits light. Further, Fig. 14 shows an example of an image display device of the present invention including the self-luminous device of the present invention. The image display device 14 shown in Fig. 14 includes a self-luminous device 3A shown in Fig. 13, and a liquid crystal panel 33A. In the image display device 140, the self-luminous device 3 is disposed behind the liquid crystal panel 33 and used as a backlight. When it is used in the image display device 14A, the voltage applied to the self-luminous device 31" is preferably 2 〇 to 35 V, and at this voltage, for example, as long as 1 〇μΑ/cm 2 is released per unit time. The electronics can be. Further, the distance between the self-luminous device 31 and the liquid crystal panel 330 is preferably about 0,1 mm. Further, as the image display device of the present invention, when the self-luminous device 31 shown in Fig. 使用 is used, it may be formed in a shape in which the self-luminous device 31 is arranged in a matrix and self-luminous The device 31 itself forms an image as an FED and displays it. At this time, the voltage applied to the self-luminous device 3 is preferably 20 to 35 V, and at this voltage, for example, electrons of 10 μΑ/cm 2 may be released per unit time. (Embodiment 5) An example of the air blowing device of the present invention using the electronic discharge element 1 of the present invention described in the first embodiment is shown in Figs. 15 and 16. Hereinafter, a case where the air blowing device of the present invention is used as a cooling device will be described. However, the use of the air blowing device is not limited to the cooling device. 136193.doc -30- 200947492 The air supply unit W shown by the circle 15 includes an electronic emission element! And a power supply 7 to which a voltage is applied. In the air blowing device (10), the electron emitting elements discharge electrons toward the electrically cooled body 41, thereby generating ion wind and cooling the object 41 to be cooled. When cooling, the voltage applied to the electron-releasing elements is preferably about 18 V. At this voltage, it is preferable to emit 1 μΑ/cm 2 of electrons per unit time under ambient gas. In the air blowing device 16 shown in Fig. 16, in addition to the air supply device shown in Fig. 5

In addition to 150, a blower fan 42 is also combined. In the air blowing device 16 shown in Fig. 16, the electron emitting element 1 discharges electrons toward the electrically cooled body 41, and the blower fan 42 blows air toward the object 41, thereby directing the electrons emitted from the electron emitting element. The object to be cooled 41 is sent to generate an ion wind to cool the object 41 to be cooled. At this time, the air volume of the blower fan 42 is preferably 0.9 to 2 L/min/cm2. Here, when the air to be cooled 41 is to be cooled by the air blowing, if the air is blown by only a fan or the like as in the prior air blowing device or the cooling device, the flow velocity of the surface of the object 41 to be cooled becomes 〇, and heat dissipation is most required. Part of the air is not displaced, so that the cooling efficiency is low. However, if the blown air contains charged particles such as electrons or ions, when it is near the vicinity of the object to be cooled 41, it is attracted to the cooled by the action of electric power. The surface of the body 41 is capable of replacing the ambient gas near the surface. Here, in the air blowing device 150' 160 of the present invention, the cooling efficiency is greatly improved by the fact that the air to be blown contains charged particles such as electrons or ions. 17 is a surface of the body 41 to be cooled when the surface of the object 41 to be cooled is blown only by the air to be cooled 41 and when the air containing the electrons and ions is blown to the object 41 to be cooled. A chart of temperature comparisons. As can be seen from Fig. 17, if the air to be blown contains electrons and ions, the cooling efficiency is improved.

As described above, the electron emission element of the present invention is characterized in that it has an electrode substrate and a thin film electrode, and electrons between the electrode substrate and the thin electrode are accelerated by applying a voltage between the electrode substrate and the thin film electrode, thereby Disposing the electrons from the thin film electrode, and providing an electron acceleration layer between the electrode substrate and the ruthenium film electrode, the electron acceleration layer comprising: conductive particles formed of a conductor and having high oxidation resistance, and An insulator material having a larger size of conductive particles. In the electron emission device of the present invention, in addition to the above configuration, the conductive fine particles may be a noble metal. As described above, when the conductive fine particles are made of noble metal, it is possible to prevent deterioration of the element including the oxidation of the conductive fine particles by the action of oxygen in the atmosphere. Thereby, the long life of the electron emission element can be achieved. In the electron emission device of the present invention, in addition to the above configuration, the conductor forming the conductive fine particles may contain at least one of gold, silver, platinum, palladium, and nickel. As described above, since the conductor forming the conductive fine particles contains at least one of gold, silver iridium, and the recording, it is possible to more effectively prevent deterioration of the element such as oxidation of the conductive fine particles by the action of oxygen in the atmosphere. . From A', it is possible to more effectively achieve a longer life of the electron emission element. In the electron emission device of the present invention, in addition to the above configuration, since the average diameter of the above-mentioned conductive fine particles is required to control the conductivity, the size thereof is required to be the above insulator material, preferably 3 to 1 Q nm. In this manner, the average enthalpy of the electric fine particles is set to be smaller than the fine particle diameter of the insulator material, and 136193.doc -32·200947492 is preferably set to 3 to 10 nm, whereby the electron acceleration layer is not formed. The conductive path of the conductive particles is difficult to cause dielectric breakdown in the electron acceleration layer. Further, in principle, there are many ambiguities, but ballistic electrons are efficiently generated by using conductive fine particles having a particle diameter within the above range.

In the electron emission device of the present invention, in addition to the above configuration, the insulator may contain at least one of Si〇2, octagonal 2〇3, and Ti〇2, or may contain an organic polymer. When at least one of Al2〇3 and Ti〇2 is contained in the insulator material, or an organic polymer is contained, the electrical resistance of the electron acceleration layer may be within an arbitrary range due to high insulation of the materials. Make adjustments. In particular, when an oxide (at least one of Si〇2, Al2〇3, and Ti〇2) is used as an insulator substance, and an electric conductor having a high oxidation resistance 3 is used as the conductive fine particles, it is more difficult to follow in the atmosphere. Oxidation under the action of oxygen causes deterioration of the element, so that the effect of stable operation from atmospheric pressure can be more clearly exhibited. Here, the insulator material may be fine particles, and the average diameter thereof is preferably Π) to HHH) nm, more preferably 12 to m nm. In this case, the dispersion state of the particle diameter may be wider than the average particle diameter. For example, for the fine particles having an average particle diameter of 5 Å, the particle size distribution is not problematic in the region of 20 to 100 nm. The average diameter of the insulator material as the fine particles is preferably from 1 Å to 150 nm, more preferably from 12 to 11 Å, whereby the inside of the charged granules can be smaller than the size of the insulator material. The heat conduction is efficiently performed to the outside to efficiently release the Joule heat generated when a current flows in the element, thereby preventing the electron emission element from being thermally damaged. It is easy to carry out the adjustment of the resistance value in the above-mentioned electron acceleration layer. 136193.doc -33 - 200947492 In the electron emission element of the present invention, in addition to the above configuration, the ratio of the above insulator substance in the electron acceleration layer is by weight The better than the timing is 80 to 95%. When the ratio of the insulator substance in the electron acceleration layer is 8 〇 to 95% by weight, the resistance value in the electron acceleration layer can be appropriately increased, thereby preventing electron emission when a large amount of electrons flow once. The component is destroyed.

In the electron emission device of the present invention, in addition to the above configuration, the layer thickness of the electron acceleration layer is preferably from 12 to 6000 nm, more preferably from 300 to 6 nm, by the layer of the electron acceleration layer. The thickness of the electron acceleration layer is uniform, and the electron acceleration layer in the layer thickness direction can be adjusted to have a thickness of Η 〇〇 、 nm, more preferably 3 〇〇 to 6 〇〇〇 nm. resistance. This result can simultaneously emit electrons from the entire surface of the surface of the electron emission element, and can efficiently emit electrons to the outside of the element. In the electronic discharge device of the present invention, in addition to the above configuration, the thin film electrode may further contain at least one of gold, silver, carbon, rhodium, titanium, and melody. By including at least one of gold, silver, charcoal, crane, chin, ming, and kiln in the thin film electrode, electrons generated in the electron acceleration layer can be efficiently worn according to the work function of the substances. As a result, more high-energy electrons are emitted to the outside of the electron emission component. In the electron emission device of the present invention, in addition to the above configuration, there may be a relatively small amount of particulate matter: insulating impurities between the electro-microparticles. In this way, when there is an insulator material of the electric particles in the vicinity of the conductive fine particles, it contributes to the improvement of the dispersibility of the conductive particles in the dispersion when the device is fabricated at 136193.doc •34-200947492. It is also possible to more effectively prevent deterioration of the element such as oxidation of the conductive fine particles by the action of oxygen in the atmosphere. Thereby, the life of the electronic emission device can be more effectively achieved. In the electron emission device of the present invention, in addition to the above-described configuration, the insulator material existing around the conductive fine particles and having a smaller size than the conductive fine particles may contain an alcoholate, a fatty acid, and a thiol in the hospital. At least one. In this way, at least one of the alcoholic material, the fatty acid, and the thiol in the insulator which is present around the conductive fine particles and having a size smaller than the conductive fine particles contributes to the improvement of the conductive fine particles during the fabrication of the device. The dispersibility in the dispersion liquid makes it difficult for the aggregate of the conductive microparticles to originate to form an abnormal path of current, and otherwise, the composition of the particles does not change with the oxidation of the conductive microparticles existing around the insulator material. Therefore, it does not affect the electronic emission characteristics. Thereby, the life of the electron emission element can be more effectively achieved. _ The four-month electronic release component tape, the insulator material existing around the conductive fine particles and having a size smaller than the conductive fine particles adhered to the surface of the conductive fine particles and exists as an adhering substance, and the attached substance may also serve as a phase The surface of the conductive fine particles is coated with an aggregate having a shape smaller than the average diameter of the conductive fine particles. In this manner, the insulator material existing around the conductive fine particles and having a smaller size than the conductive fine particles adheres to the surface of the conductive fine particles or covers the conductive body as an aggregate smaller than the average of the conductive fine particles. The surface of the microparticles #This helps to improve the scatterability of the conductive particles in the dispersion of the component 136I93.doc -35· 200947492 in the production of the component. Therefore, it is more difficult to form the aggregate of the conductive particles. / / / / / In addition to this, since the change in particle composition does not occur with the oxidation of the conductive fine particles existing around the insulator material, it does not affect the electron emission characteristics. Thereby, the life of the electron emission element can be more effectively achieved. Further, in the electron emission device of the present invention, the insulator material having a size larger than that of the conductive fine particles may be formed on the electrode substrate, and may have a plurality of openings penetrating through the thickness direction of the layer, the opening The conductive particles + can be accommodated in the portion. Since the insulator material which is formed into a sheet shape is not an aggregate of fine particles but exists as a solid block, it functions as an insulator in which no current flows. On the other hand, in the portion where the conductive fine particles are accommodated in the opening portion, the surface resistance is lowered, and only a portion of the conductive current is likely to flow. As a result, only the portion of the opening portion in which the conductive fine particles are contained generates electron emission. In this method, it is not necessary to uniformly apply the production step of dispersing the dispersion-dispersed liquid, so that a larger-area electron emission element can be easily formed. The electronic discharge device of the present invention includes any one of the above-described electron emission devices and a power supply unit that applies a voltage between the electrode substrate and the thin film electrode. According to the above configuration, electrons can be stably released not only in a vacuum but also in an atmospheric pressure. Further, electrons can be emitted without generating harmful substances such as ozone or N0x. Further, the electronic emission device of the present invention is used in a self-luminous device and an image display device having the same, whereby a 136193.doc-36-200947492 vacuum seal can be provided in the atmosphere. A long-life surface emitting light-emitting device can be realized. In addition, the electronic discharge element of the present invention is used for a blower or a cooling device so as not to be accompanied by discharge, and does not produce (4) quality, which is led by ozone or helium, and can be high by utilizing the slippery effect of the surface of the object to be cooled. Cooling efficiently _. Further, the electronic discharge element of the present invention is used for a charging device and an image forming device of the charging device, so that the discharge is not accompanied, and the harmful substance f led by ozone or helium is generated, and The charged body can be charged. Further, when the electron emission device of the present invention is used in an electron beam curing device, electron beam hardening can be performed in a large area, and it is possible to achieve a low cost and high mass production. In order to solve the above problems, in the method of manufacturing an electron emission element of the present invention, the electron emission element has an electrode substrate and a thin film electrode, and the electrode substrate and the film are made by applying electricity between the electrode substrate and the film electrode. The electrons between the electrodes are accelerated to cause the electrons to be emitted from the thin film electrode. The method includes the steps of: forming an electron acceleration layer on the electrode substrate to form an electron acceleration layer, the electron acceleration layer comprising: Conductive fine particles formed by the body and having high oxidation resistance, and an insulator material having a larger size than the conductive fine particles; and a thin film electrode forming step of forming the thin film electrode on the electron acceleration layer. According to the above method, it is possible to produce an electron emission element which can stably emit electrons not only in a vacuum but also under atmospheric pressure, and which hardly generates ozone or N0x harmful substances such as 136193.doc • 37·200947492. The electron acceleration layer forming step may further include: a mixing step of mixing the conductive fine particles and the insulator material in a solvent to form a mixed substance; and a coating step of coating on the electrode substrate. a mixed substance; and a drying step of drying the above-mentioned coated mixture. Alternatively, the electron acceleration layer forming step may further include a lamination step of laminating the insulator material having a plurality of openings passing through the lamination direction on the electrode substrate, and a filling step of The opening portion is filled with the conductive fine particles. Alternatively, the electron acceleration layer forming step may further include: a layer forming step of forming the insulator material layer on the electrode substrate; and an opening step of forming a plurality of layers extending in a thickness direction of the layer on the insulator material An opening portion; and a filling step of filling the opening portion with the conductive fine particles. The specific embodiments of the present invention and the specific embodiments of the present invention are merely intended to be illustrative of the technical scope of the present invention, and are not limited to such specific examples and are narrowly understood. The spirit and the scope of the patent application described below can be implemented in various ways. It is a matter of course that the scope of the invention is not limited to the scope of the invention. [Industrial Applicability] The electron emission element of the present invention is not accompanied by discharge, so that ozone is not generated and can be stably operated at atmospheric pressure. Therefore, it can be preferably applied to, for example, an image forming machine such as an electronic photocopying machine, a printing machine, a facsimile machine, etc., a charging device of an apparatus or an electron beam hardening device, or a combination with an illuminant. An image display device or an air blowing device that generates an ion wind by using the emitted electrons. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the configuration of an electron emitting element according to an embodiment of the present invention. Figure 2 is an enlarged view of a cross section of the vicinity of the fine particle layer in the electron emission element of Figure 1. Figure 3 is a diagram showing the measurement system of the electron emission experiment. Fig. 4 is a view showing a graph of electron emission current in a vacuum. Fig. 5 is a graph showing a graph of current in the element when electrons are discharged in a vacuum. Fig. 6 is a view showing a graph of electron emission current in the atmosphere and current in the element. Fig. 7 is a graph showing the change of the electron emission current in the atmosphere and the current change in the current in the element. Fig. 8 is an enlarged view showing a cross section of the vicinity of an electron acceleration layer of another configuration of the electron emission element of the present invention. Fig. 9 is a view showing an example of a charging device using the electronic discharge element of the present invention. Fig. 10 is a view showing an example of an electron beam curing apparatus using the electron emitting element of the present invention. Fig. 11 is a view showing an example of a self-luminous device using the electron emission element of the present invention. 136193.doc -39· 200947492 Fig. 12 is a view showing another example of a self-luminous device using the electron emission element of the present invention. Figure 13 is a view showing still another example of a self-luminous device using the electron emission element of the present invention. Fig. 14 is a view showing another example of an image forming apparatus including a self-luminous device using the electron emitting element of the present invention. Fig. 15 is a view showing an example of a cooling device using the electronic discharge element of the present invention and a cooling device including the air blowing device. Fig. 16 is a view showing another example of a device using the electronic discharge element of the present invention and a cooling device including the air blowing device. Fig. 17 is a graph showing a comparison between a case where air is blown to a body to be cooled and a case where air is blown by ions and ions. [Description of main component symbols] 1 ' Γ Electron emission component 2 Substrate (electrode substrate) 3 Upper electrode (thin film electrode) 4 Microparticle layer (electron acceleration layer) 4' Electron acceleration layer 5 Insulator microparticles (insulator substance) 5' Insulator substance 6 Metal particles (conductive particles) 7 Power supply (power supply unit) 8 Counter electrode 9 Insulator spacer 136193.doc -40- 200947492

11 21 22 31 ' 3Γ ' 31" 32, 32' 33 34 35 36 41 42 51 90 100 140 150 160 330 Photoreceptor Accelerating electrode photoresist Self-illuminating device Fluorescent body 1TO film Glass substrate Power supply Light-emitting part is cooled by air Fan opening part charging device electron beam curing device image display device air supply device air supply device liquid crystal panel 136193.doc -41 -

Claims (1)

200947492 X. Application for Patent Park: 1. An electronic emission device characterized in that it has an electrode substrate and a thin film electrode, and a voltage is applied between the SHA electrode substrate and the thin film electrode to cause electrons at the electrode Accelerating between the substrate and the thin film electrode to release the electrons from the thin film electrode, and an electron accelerating layer is disposed between the electrode substrate and the thin film electrode, comprising: a conductive material formed of a conductive body and having high oxidation resistance Microparticles; and & insulator materials having a size larger than that of the above-mentioned conductive microparticles. 2. The electron emission element of claim 1, wherein the conductive fine particles are noble metals. 3. The electron emission device of claim 1 or 2, wherein the conductor forming the conductive fine particles contains at least one of gold, silver, platinum, palladium, and nickel. 4. The electronic emission device of any one of clause 3, wherein the conductive particles have an average diameter of 3 to 1 〇 nm. 5. The electron emission device according to any one of claims 1 to 4, wherein the insulator material contains at least one of Si〇2, aI2〇3, and TiO2 or contains an organic polymer. 6. The electron emission element according to any one of claims 1 to 5, wherein the insulator material is fine particles having an average diameter of 10 to 1000 nm. -7. The electron emission element of claim 6, wherein the insulator material as the fine particles has an average diameter of 12 to 110 nm. 8. The electron emission element according to any one of claims 1 to 7, wherein 136193.doc 200947492 the above-mentioned insulator substance in the electron acceleration layer has a ratio of 80 to 95% by weight. 9. The electron emission device according to any one of claims 1 to 8, wherein the electron acceleration layer has a layer thickness of 12 to 6 Å. 10. The electron emission device of claim 9, wherein the electron acceleration layer has a layer thickness of 3 〇〇 6 6 〇〇〇 nm. 11. The electron emission device of any one of claims 1 to 1, wherein the thin film electrode contains at least β of gold, silver, carbon, tungsten, titanium, aluminum, and palladium. 12. The electron emission device of any one of the preceding claims, wherein an insulator material having a size smaller than a size of the conductive microparticles is present around the conductive microparticles. 13. The electron emission device of claim 2, wherein the insulator material having a size smaller than a size of the conductive fine particles present in the conductive fine particles contains at least one of an alcoholate, a fatty acid, and alkanethiol. The electron emission element according to any one of the preceding claims, wherein the insulator material having a size larger than that of the conductive fine particles is formed on the electrode substrate to form a layer and has a plurality of layers penetrating through the thickness direction of the layer. An opening; the conductive fine particles are accommodated in the opening. An electron emission device comprising: the electron emission device according to any one of claims 1 to 14, and a power supply 136193.doc 200947492 for applying a voltage between the electrode substrate and the thin film electrode. 16. A self-luminous device, comprising: an electron emission device according to claim 15 and an illuminant. 17. An image display device characterized by comprising - a self-luminous device as claimed in claim 16. An air blowing device comprising: the electronic discharging device of claim 15 and blowing electrons under ambient gas. A cooling device characterized by comprising: an electronic discharge device as claimed in claim 15 and blowing electrons under ambient gas to cool the object to be cooled. 20. A charging device comprising: an electronic discharging device as claimed in claim 15 for charging a photoreceptor. A 21' type image forming apparatus, comprising: a charging device as claimed in claim 20. An electron beam hardening apparatus comprising: the electronic discharge apparatus of claim 15. 23. A method of manufacturing an electron emission element, characterized in that the electron emission element has an electrode substrate and a thin film electrode 'by applying a voltage between the electrode substrate and the thin film electrode to cause electrons on the electrode substrate and the thin film electrode Accelerating between and releasing from the thin film electrode, the manufacturing method thereof comprises: an electron accelerating layer forming step of forming an electron accelerating layer on the electrode substrate, the electron accelerating layer comprising: an electric conductor formed and resistant to oxygen 136193 .doc 200947492 A conductive material having a high chemical power, an insulator material having a size larger than that of the conductive fine particles, and a thin film electrode forming step of forming the thin film electrode on the electron acceleration layer. The method of manufacturing the electron emission element of claim 23, wherein the electron acceleration layer forming step comprises: a mixing step of: mixing the conductive fine particles with the insulator material by a solvent to form a mixed substance; and a coating step Applying the mixed substance to the electrode substrate; and drying step of drying the applied mixture. 25. The method of manufacturing an electron emission element according to claim 23, wherein the electron acceleration layer forming step comprises: a lamination step of laminating the insulator material having a plurality of openings extending in a lamination direction to the electrode And a φ filling step of filling the conductive fine particles into the opening. The method of manufacturing an electron emission element according to claim 23, wherein the electron acceleration layer forming step comprises: a layer forming step of forming the insulator material on the electrode substrate; and an opening step of the insulator material A plurality of openings that penetrate the thickness direction of the layer are formed thereon, and a filling step of filling the conductive fine particles into the opening. 136193.doc